Benzotriazole derivative compound

ABSTRACT

Provided are benzotriazole derivative compounds of the general formula that are novel compounds capable of strongly absorbing light in the ultraviolet range, particularly 300-330 nm, while strongly absorbing light in the visible light short-wavelength range up to around 450 nm and being used suitably as a light absorber having high light fastness with a light-blocking function over an extended period of time. [Preferably, R 1  is a hydrogen atom or alkyl group, R 2  is a C1-8 alkyl group, R 3  is a hydrogen atom, alkyl group, acryloyloxyalkyl group, or methacryloyloxyalkyl group].

TECHNICAL FIELD

The present invention relates to a new benzotriazole derivativecompound. The present invention also relates to a light absorber and aresin composition that includes the new benzotriazole. In more detailthe present invention relates to a light absorber and a resincomposition capable of strongly absorbing an ultraviolet light and avisible light short wavelength range by exhibiting a maximum absorptionwavelength in a vicinity of 310 nm and 380 nm.

BACKGROUND ART

It is well known that organic materials such as a resin and the likedegrade by a function of ultraviolet light of solar light. In the resin,coloration or decrease in strength occurs by the ultraviolet light, andin a variety of functional organic materials, decomposition is caused bythe ultraviolet light and their functions degrade.

In order to prevent the degradation of these organic materials caused bythe ultraviolet light, an ultraviolet light absorber is generally used.For example, in a display device, it is generally practiced to add theultraviolet light absorber to optical films such as polarizer protectivefilms and the like thereby preventing the coloration of these opticalfilms. Also, in order to prevent the degradation of a near-infraredlight absorber included in anti-reflection films caused by theultraviolet light, the ultraviolet light absorber is added to theanti-reflection films. Further, a variety of organic materials such asfluorescent elements, phosphorescent elements, and the like are used ina luminous element of organic EL displays. That is to say, in order toprevent the degradation of the organic materials caused by theultraviolet light, the ultraviolet absorber is added to a surface filmof the display.

In human bodies, it is well known that skins and eyeballs get tanned bythe ultraviolet light, causing various maladies. The bad effect to theeyeballs caused by the ultraviolet light includes, for example, apossible development of a cornea inflammation when the eyes are exposedto solar light in such an outdoor place where there are lots ofultraviolet light. As for the bad effect to lens, a cataract might bedeveloped by the accumulated ultraviolet light.

In order to prevent various diseases related to eyeballs caused by theultraviolet light, it is generally practiced to add the ultravioletabsorber to glass lens or contact lens, thereby preventing theultraviolet light from reaching the eyes.

Further, recently, it has been pointed out that among solar lights, notonly the ultraviolet light of not greater than 400 nm but also the lightof visible light short wavelength range of around 400 to 450 nm maybadly affect human bodies, and for the specific uses including the abovementioned use, such a light absorber is required that can absorb thelight of visible light long wavelength range.

For each of the above mentioned uses, some light absorbers have beenproposed that efficiently absorb the ultraviolet light and the light ofvisible light short wavelength range, and as compounds that have anabsorbing function in such a wavelength range, for example, as describedin Patent Documents 1 to 2, indole derivative, pyrrolidine-amidederivative, and xanthon derivative are exemplified. However, in general,these compounds have low light resistance property and therefore, theydegrade by being exposed to solar light and have low light absorbingcapability. Thus, they cannot be used for a long period of time.Further, Patent Documents 1 to 2 have no descriptions on lightresistance property.

Patent documents 3 to 4 propose a light absorber capable of efficientlyabsorbing the ultraviolet light and the light of the short wavelengthrange, by modifying benzotriazole with sesamol that is generally knownto have high light resistance. However, such a light absorber is weak inabsorbing the light of not less than 420 nm although it does absorb thevisible light short wavelength range. It also has a weakness in itscapability of absorbing ultraviolet light range in the vicinity of 300to 330 nm.

PRIOR ART DOCUMENTS Patent Documents

-   Patent document 1: Official Gazette, Patent Publication No2012-58643-   Patent document 2: Official Gazette, Patent Publication    No2007-284516-   Patent Document 3: Official Gazette, Patent Publication No2012-41333-   Patent Document 4: Official Gazette, Patent Publication No2012-25680

SUMMARY OF THE INVENTION Problem to be Solved by the Invention

In view of the above situations, the object of the present invention isto provide a new compound capable of preferably being used as a lightabsorber that absorbs strongly the ultraviolet light range in particularof 300 to 330 nm to show a high light resistance having a light blockingfunction in a long term range, while strongly absorbing ultraviolet thelight of visible light short wavelength range to the vicinity of 450 nm.

Means to Solve the Problem

In the present invention, the main means to solve the above mentionedproblem is providing a new benzotriazole derivative compound asrepresented by the following general formula (1).

[in the general formula (1), R₁ represents a hydrogen atom or an alkylgroup whose carbon number is 1 to 8, R₂ represents a hydrogen atom, analkyl group whose carbon number is 1 to 18, a carboxyalkyl group whosealkyl carbon number is 1 to 7, an alkyl oxycarbonylalkyl group of whicha total alkyl carbon number is 2 to 15, an acryloyl oxyalkyl group whosealkyl carbon number is 1 to 4, an acryloyl oxyhydroxyalkyl group whosealkyl carbon number is 1 to 4, a methacryloyl oxyalkyl group whose alkylcarbon number is 1 to 4, or a methacryloyl oxyhydroxyalkyl group whosealkyl carbon number is 1 to 4, R₃ represents a hydrogen atom or an alkylgroup whose carbon number is 1 to 18, a carboxyalkyl group whose alkylcarbon number is 1 to 7, an alkyloxycarbonylalkyl group of which a totalalkyl carbon number is 2 to 15, a hydroxyalkyl group whose carbon numberis 1 to 8, an alkylcarbonylalkyl group of which a total alkyl carbonnumber is 2 to 15, phenyl group, tolyl group, an acryloyl oxyalkyl groupwhose alkyl carbon number is 1 to 4, an acryloyl oxyhydroxyalkyl groupwhose alkyl carbon number is 1 to 4, a methacryloyl oxyalkyl group whosealkyl carbon number is 1 to 4, or a methacryloyl oxyhydroxyalkyl groupwhose alkyl carbon number is 1 to 4.]

In benzotriazole compound represented by the above general formula (1),it is preferable that R₁ represents a hydrogen atom or an alkyl groupwhose carbon number is 1 to 8, that R₂ is an alkyl group whose carbonnumber is 1 to 8, and that R₃ represents a hydrogen atom or an alkylgroup whose carbon number is 1 to 8, or an acryloyloxyalkyl group whosealkyl carbon number is 1 to 2 or a methacryloyloxyalkyl group whosealkyl carbon number is 1 to 2.

Effect of the Invention

Benzotriazole derivative compound represented by general formula (1) ofthe present invention has a carboxyl group in the 5th position of abenzotriazole ring and also has a hydroxy group or an alcoxy group inthe para position of a phenolic ring, and therefore, it shows a maximumabsorbing wavelength in the vicinity of 310 nm and 380 nm to stronglyabsorb the ultraviolet light and the visible light short wavelengthrange, and has a high light-resistance that shows the light blockingfunction in a long term. Therefore, the benzotriazole derivativecompound of the present invention is useful as a light absorber capableof solving the problem that the prior art used to have.

Best Embodiment for Carrying Out the Invention

Hereinafter, the detailed explanations are given for the presentinvention. In the present invention, as an ultraviolet light absorberand as a resin composition, benzotriazole derivative compoundrepresented by general formula (1) is used. Hereinafter, theexplanations are given for the compound represented by general formula(1).

In general formula (1), R₁ exemplifies a hydrogen atom or a linear orbranched alkyl group, etc whose carbon number is 1 to 8 such as methylgroup, ethyl group, propyl group, isopropyl group, butyl group, isobutylgroup, sec-butyl group, tert-butyl group, hexyl group, octyl group,2-ethylhexyl group, etc, R₂ exemplifies a hydrogen atom or a linear orbranched alkyl group, etc whose carbon number is 1 to 18 such as methylgroup, ethyl group, propyl group, isopropyl group, butyl group, isobutylgroup, sec-butyl group, tert-butyl group, hexyl group, octyl group,2-ethylhexyl group, dodecyl group, octadecyl group, etc; carboxyalkylgroup whose alkyl carbon number is 1 to 7, such as carboxyethyl group,carboxyheptyl group, etc; an alkyl oxycarbonylalkyl group of which atotal of each alkyl carbon number is 2 to 15 such as methoxycarbonylethyl group, octyloxycarbonyl heptyl group, etc; a hydroxyalkyl groupwhose carbon number is 1 to 8, such as hydroxyethyl group, hydroxyoctylgroup, etc; an alkylcarbonyloxyalkyl group of which a total of eachalkyl carbon number is 2 to 15, an acryloyloxyalkyl group whose alkylcarbon number is 1 to 4, such as an acryloyloxyethyl group, anacryloyloxybutyl group, etc; a methacryloyloxyalkyl group whose alkylcarbon number is 1 to 4, such as a methacryloyloxyethyl group, amethacryloyloxybutyl group; or a methacryloyloxyhydroxyalkyl group whosealkyl carbon number is 1 to 4, such as methacryloyloxy-2-hydroxypropylgroup, etc, and R₃ exemplifies a hydrogen atom or a linear or branchedalkyl group, etc whose carbon number is 1 to 18 such as methyl group,ethyl group, propyl group, isopropyl group, butyl group, isobutyl group,sec-butyl group, tert-butyl group, hexyl group, octyl group,2-ethylhexyl group, dodecyl group, octadecyl group, etc; carboxyalkylgroup whose alkyl carbon number is 1 to 7, such as carboxyethyl group,carboxyheptyl group, etc; an alkyl oxycarbonylalkyl group of which atotal of each alkyl carbon number is 2 to 15 such as methoxycarbonylethyl group, octyloxycarbonylheptyl group, etc; a hydroxyalkyl groupwhose carbon number is 1 to 8, such as hydroxyethyl group, hydroxyoctylgroup, etc; an alkylcarbonyloxyalkyl group of which a total of eachalkyl carbon number is 2 to 15, such as methoxycarbonyl ethyl group,octyloxycarbonylheptyl group, etc; a hydroxyalkyl group whose carbonnumber is 1 to 8, such as hydroxyethyl group, hydroxyoctyl group, etc;an alkylcarbonyloxyalkyl group of which a total of each alkyl carbonnumber is 2 to 15 such as a methylcarbonyloxyethyl group, aheptylcarbonyloxyoctyl group, etc; a phenyl group, a tolyl group, anacryloyloxyalkyl group whose alkyl carbon number is 1 to 4, such as anacryloyloxyethyl group, an acryloyloxybutyl group, etc; anacryloyloxyhydroxy group whose alkyl carbon number is 1 to 4, such asacroyloxy-2-hydroxypropyl group, etc; a methacryloyloxyalkyl group whosealkyl carbon number is 1 to 4, such as a methacryloyloxybutyl group,etc; or a a methacryloyloxyalkyl group whose alkyl carbon number is 1 to4, such as a methacroyloxy-2-hydroxypropyl group, etc.

In benzotriazole compound represented by the above general formula (1),it is preferable that R₁ represents a hydrogen atom or an alkyl groupwhose carbon number is 1 to 8, that R₂ is an alkyl group whose carbonnumber is 1 to 8, and that R₃ represents a hydrogen atom or an alkylgroup whose carbon number is 1 to 8, or an acryloyloxyalkyl group whosealkyl carbon number is 1 to 2 or a methacryloyloxyalkyl group whosealkyl carbon number is 1 to 2.

As general formula (1) of the benzotriazole derivative compound of thepresent invention, the following can be exemplified. Methyl2-(2-hydroxy-5-methoxyphenyl)-2H-benzotriazole-5-carboxylate, methyl2-(3-tert-butyl-2-hydroxy-5-methoxyphenyl)-2H-benzotriazole-5-carboxylate,methyl2-(2-hydroxy-5-methoxy-3-tert-octylphenyl)-2H-benzotriazole-5-carboxylate,octyl2-(3-tert-butyl-2-hydroxy-5-methoxyphenyl)-2H-benzotriazole-5-carboxylate,2-ethylhexyl2-(3-tert-butyl-2-hydroxy-5-methoxyphenyl)-2H-benzotriazole-5-carboxylate,octyl2-(3-tert-butyl-2-hydroxy-5-methoxyphenyl)-2H-benzotriazole-5-carboxylate,methyl 2-[3-tert-butyl-2-hydroxy-5-(2-methacryloyloxyethoxy)phenyl]-2H-benzotriazole-5-carboxylate, phenyl2-(3-tert-butyl-2-hydroxy-5-methoxyphenyl)-2H-benzotriazole-5-carboxylate,2-methacryloyloxyethyl2-(2-hydroxy-5-methoxyphenyl)-2H-benzotriazole-5-carboxylate,2-acryloyloxyethyl2-(3-tert-butyl-2-hydroxy-5-methoxyphenyl)-2H-benzotriazole-5-carboxylate,2-methacryloyloxyethyl2-(3-tert-butyl-2-hydroxy-5-methoxyphenyl)-2H-benzotriazole-5-carboxylate.

Although a method of synthesizing general formula (1) of thebenzotriazole derivative compound of the present invention is notspecifically limited and a publicly known reaction principle an widelybe used, it can be synthesized through the reaction formula shown in thefollowing (chemicals 2 to 7), for example.

In the benzotriazole derivative compounds of the present invention,regarding those having a polymerizable double bond, homopolymerizationor copolymerization are possible. Although other copolymerizablepolymers are not specifically limited, for example, acrylic ester suchas methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate,hexyl acrylate, octyl acrylate, or methacrylic ester such as methylmethacrylate, ethyl methacrylate, propyl methacrylate, butylmethacrylate, hexyl methacrylate, octyl methacrylate, can beexemplified.

Although the resin to which the benzotriazole derivative compound of thepresent invention may be added is not specifically limited, α olefinpolymer or ethylene-vinyl acetate copolymer such as polyethylene,polypropylene, polybutene, polypentene, poly-3-methyl butylene, andpolymethyl pentene, polyolefin such as ethylene-propylene copolymer,polyvinyl chloride, polyvinyl bromide, polyvinyl fluoride, chlorinatedpolyethylene, chlorinated polypropylene, brominated polyethylene,chlorinated rubber, vinyl chloride-vinyl acetate copolymer, vinylchloride-ethylene copolymer, vinyl chloride-propylene copolymer, vinylchloride-styrene copolymer, vinyl chloride-isobutylene copolymer, vinylchloride-vinylidene copolymer, vinyl chloride-styrene-maleic anhydrideternary copolymer, vinyl chloride-styrene-acrylonitrile ternarycopolymer, vinyl chloride-butadiene copolymer, vinylchloride-isobutylene copolymer, vinyl chloride-chlorinated propylenecopolymer, vinyl chloride-vinylidene chloride-vinyl acetate ternarycopolymer, vinyl chloride-acrylic ester copolymer, vinyl chloride-maleicester copolymer, vinyl chloride-methacrylate ester copolymer, vinylchloride-acrylonitrile copolymer, halogen containing synthetic resinsuch as internal plasticity polyvinyl chloride, petroleum resin,coumarone resin, polystyrene, copolymer of styrene and other monomer(such as maleic anhydride, butadiene, acrylonitrile), styrene resin suchas acrylonitrile-butadiene-styrene resin, acrylicester-butadiene-styrene resin, and methacrylic ester-butadiene-styreneresin, polyvinyl acetate, polyvinyl alcohol, polyvinyl formal, polyvinylbutyral, acrylic resin, methacrylic resin, polyacrylonitrile,polyphenylene oxide, polycarbonate, denaturalized polyphenylene oxide,polyacetal, phenolic resin, urea resin, melamine resin, epoxy resin,silicone resin, polyethylene terephthalate, reinforced polyethyleneterephthalate, polybutyrene terephthalate, polysulfone resin, polyethersulfone, polyphenylene sulfide, polyether ketone, polyether imide,polyixy benzoile, polyimide, polymareimide, polyamide imide, alkydresin, amino resin, vinyl resin, er soluble resin, powder paint resin,polyamide resin, polyurethane resin, polythiourethane resin, unsaturatedpolyester resin can be exemplified.

In adding the benzotriazole derivative compound of the present inventionto a resin, as an ultraviolet light absorber, only the benzotriazolederivative compound of the present invention can be used or it can beused in combinations with other ultraviolet light absorbers. Regardingultraviolet light absorbers other than the benzotriazole derivativecompound of the present invention, they are not specifically limited andthey can be used as far as they can be obtained in general markets andas far as they can absorb the ultraviolet region. For example,benzotriazole derivatives, benzophenone derivatives, salicylatederivatives, cyanoacrylate derivatives, triazine derivatives and thelike are used. The ultraviolet light absorber can be used alone or twoor more of them can be mixed together, as appropriate.

The benzotriazole derivative compound of the present invention can beused by 0.01 to 10 wt % with respect to the resin, and preferably by 0.1to 1 wt % with respect to the resin.

EXAMPLES

Hereinafter, a method of synthesizing the benzotriazole derivativecompound experimented in the present invention, and properties of thecompound are shown. However, the present invention is not limited tothese embodiments.

Example 1 Synthesis of compound (a); 2-methacryloyloxyethyl2-(3-tert-butyl-2-hydroxy-5-methoxyphenyl)-2H-benzotriazole-5-carboxylate

To a four-neck flask of 200 ml, a balled condenser, a thermometer, and amixing device were attached, in which 100 ml of water, 6.5 g (0.061 mol)of sodium carbonate, 20.0 g (0.110 mol) of 4-amino-3-nitro benzoic acidwere put and dissolved, to which 22.7 g (0.118 mol) of an aqueoussolution of 36% sodium nitrite were added. To a four-neck flask of 500ml, a balled condenser, a thermometer, and a mixing device wereattached, in which 100 ml of water and 43.0 g (0.274 mol) of 62.5%sulfuric acid and cooled to 3 to 7° C., onto which the mentionedsolution was dripped, followed by mixing it at the same temperature for2 hours to obtain an aqueous solution of diazonium salt. To a four-neckflask of 1000 ml, a balled condenser, a thermometer, and a mixing devicewere attached, in which 18.0 g (0.100 mol) of2-tert-butyl-4-methoxyphenol, 10 ml of isopropyl alcohol, and 140 ml ofwater were put and mixed, onto which an aqueous solution of diazoniumsalt was dripped at 5 to 10° C. for 2 hours, further followed by mixingfor 12 hours at 10 to 15° C. to obtain a slurry liquid of2-tert-butyl-6-(4-carboxy-2-nitrophenylazo)-4-methoxyphenol. 27.8 g(0.222 mol) of an aqueous solution of 32% sodium hydroxide and 200 ml ofisopropyl alcohol were added thereto, followed by removing a water layerin a bottom layer at 70° C. 30.0 g (0.222 mol) of an aqueous solution of32% sodium hydroxide, 200 ml of water, and 0.4 g of hydroquinone wereadded thereto, followed by dripping 6.0 g (0.072 mol) of 60%hydraxine-hydrate at 40 to 50° C. for 1 hour, followed by mixing at thesame temperature for 2 hours. Then the pH value was adjusted to 4 by62.5% sulfuric acid, followed by filtering, rinsing, and drying thegenerated sediment to obtain 23.6 g of5-carboxy-2-(3-tert-butyl-2-hydroxy-5-methoxyphenyl)-2H-benzotriazoleN-oxide.

To a four-neck flask of 500 ml, a balled condenser, a thermometer, and amixing device were attached, in which 23.6 g (0.066 mol) of5-carboxy-2-(3-tert-butyl-2-hydroxy-5-5methoxyphenyl)-2H-benzotriazole Noxide, 100 ml of isopropyl alcohol, 100 ml of water, and 24.0 g (0.192mol) of an aqueous solution of 32% sodium hydroxide were put, to which12.0 g (0.111 mol) of a thiourea dioxide was added at 70 to 80° C.taking for 3 hours. It was mixed at the same temperature for 1 hour,followed by removing the water layer in the bottom layer by separatingit, followed by adjusting the pH value to 4 by using 62.5% sulfuricacid, further followed by filtering, rinsing, and drying the generatedsediment, thereby obtaining 20.3 g of5-carboxy-2-(3-tert-butyl-2-hydroxy-5-5methoxyphenyl)-2H-benzotriazole.

To a four-neck flask of 300 ml, a balled condenser, a thermometer, and amixing device were attached, to which 20.3 g (0.059 mol) of5-carboxy-2-(3-tert-butyl-2-hydroxy-5-5methoxyphenyl)-2H-benzotriazole,100 ml of toluene, 13.0 g (0.109 mol) of thionyl chloride, and 2.0 ml ofN,N-dimethylformamide were put and were mixed at 60 to 70° C. for 3hours. Subsequently, by depression, the solvent was recovered, followedby adding 100 ml of toluene, 14.0 g (0.108 mol) of methacrylic acid2-hydroxyethyl, and 8.3 g (0.105 mol) of pyridine, and were mixed at 60to 70° C. for 1 hour. 20 ml of water and 9.0 g (0.057 mol) of 62.5%sulfuric acid were added thereto and the water layer of the bottom layerwere separated at 60 to 70° C. and removed, followed by recovering thetoluene by depression, to which 90 ml of isopropyl alcohol was added,further followed by filtering, rinsing, and drying the generatedsediment thereby obtaining a coarse crystal. This coarse crystal wasrecrystalized to obtain 22.2 g of compound (a). The yield was 49% (from2-tert-butyl-4-methoxyphenol). A melting point was 124° C.

In the meantime, by HPLC analysis, a purity of the compound (a) wasmeasured.

<Condition of Measurement>

Apparatus: L-2130 (Hitachi High-Technologies Corporation)

Column used: SUMIPAX ODS A-212 6.0×150 mm 5 μm

Column temperature: 40° C.

Mobile phase: methanol/water=95/5 (3 ml phosphoric acid/L)

Flow velocity: 1.0 ml/min

Detection: UV250 nm

<Result of Measurement>

HPLC surface purity: 98.5%

For information, the HPLC measurement was conducted under the samemeasurement condition as above in the following Examples 2 to 5.

The ultraviolet-visible absorption spectrum of the compound (a) wasmeasured, and it was found that the maximum absorption wavelength λmaxwas 313.2 nm and 382.8 nm, respectively, and the molar extinctioncoefficient ε of the wavelength was 14800 and 12700, respectively. Thespectrum is shown in FIG. 1. The measurement condition of the spectrumis as follows:

<Condition of Measurement>

Apparatus: UV-2450 (Shimadzu Corporation)

Measurement wavelength: 250 to 500 nm

Solvent: chloroform

Concentration: 10 ppm

For information, the ultraviolet-visible absorption spectrum wasmeasured under the same measurement condition as above in the followingExamples 3 to 6.

Further, as the result of the NMR measurement of the compound (a), theabove structure was supported. The measurement condition is as follows:

<Condition of Measurement>

Apparatus: JEOL JNM-AL300

Resonant frequency: 300 MHz (1H-NMR)

Solvent: chloroform-d

As an internal standard substance of 1H-NMR, tetramethylsilane was used,and the chemical shift value was represented by δ value (ppm) and thecoupling constant was represented by Hertz. Further, s represents anabbreviation of singlet, d that of doublet, t that of triplet, and mthat of multiplet. The same is applied to the following Examples 2 to 6.For information, in the following Examples 2 to 6, the NMR measurementwas conducted as in the present Example. The content of the NMR spectrumobtained is as follows:

δ=11.44 (s, 1H, phenol-OH), 8.73 (m, 1H, benzotriazole-H), 8.13 (d, 1H,J=9.0 Hz, benzotriazole-H), 7.98 (d, 1H, J=11.1 Hz, benzotriazole-H),7.82 (s, 1H, phenol-H), 7.05 (s, 1H, phenol-H), 6.18 (s, 1H, C═CH₂—H),5.62 (s, 1H, C═CH₂—H), 4.65 (m, 2H, methacryloyl-O—CH₂—H), 4.56 (m, 2H,benzotriazole-CO—O—CH₂—H), 3.93 (s, 3H, phenol-O—CH₃—H), 1.98 (s, 3H,CH₂═—C—CH₃—H), 1.56 (s, 9H, tert-butyl-H)

Example 2 [Synthesis of compound [b]; 2-acryloyloxyethyl2-(3-tert-butyl-2-hydroxy-5-methoxyphenyl)-2H-benzotriazole-5-carboxylate]

Compound (b) was obtained with the yield of 46% (from2-tert-butyl-4-methoxyphenyl) in the same manner as in Example 3 exceptthat acrylate acid 2-hydroxyethyl was used instead of methacrylate acid2-hydroxyethyl. The melting point was 126° C. and the HPLC surfacepurity was 98.1%.

Further, when the ultraviolet-visible absorption spectrum of thecompound (b) was measured, the maximum absorption wavelength λmax was313.2 nm and 380.6 nm, respectively, and the molar extinctioncoefficient E of the wavelength was 15400 and 13100, respectively. Thespectrum is shown in FIG. 2. The measurement condition of the spectrumis as follows:

<Condition of Measurement>

Apparatus: UV-1850 (Shimadzu Corporation)

Measurement wavelength: 250 to 500 nm

Solvent: chloroform

Concentration: 10 ppm

Further, as the result of the NMR measurement of the compound (b), theabove structure was supported. The measurement condition is as follows:

δ=11.39 (s, 1H, phenol-OH), 8.72 (s, 1H, benzotriazole-H), 8.12 (d, 1H,J=9.0 Hz, benzotriazole-H), 7.96 (d, 1H, J=9.0 Hz, benzotriazole-H),7.81 (s, 1H, phenol-H), 7.05 (s, 1H, phenol-H), 6.46 (m, 1H, CH═CH₂—H),6.20 (m, 1H, CH₂═CH—H), 5.89 (m, 1H, CH═CH₂—H), 4.64 (m, 2H,acryloyl-O—CH₂—H), 4.57 (m, 2H, acryloyl-O—CH₂—C—H₂—H), 3.81 (s, 3H,phenol-O—CH₃—H), 1.50 (s, 9H, tert-butyl-H)

Example 3 Synthesis of compound (c); methyl2-(3-tert-butyl-2-hydroxy-5-methoxyphenyl)-2H-benzotriazole-5-carboxylate

Compound (c) was obtained with the yield of 53% (from2-tert-butyl-4-methoxyphenyl) in the same manner as in Example 1 exceptthat methyl alcohol was used instead of methacrylate acid2-hydroxyethyl. The melting point was 154° C. and the HPLC surfacepurity was 99.4%. The maximum absorption wavelength A max was 312.6 nmand 381.6 nm, respectively, and the molar extinction coefficient ε ofthe wavelength was 14800 and 13000, respectively. The spectrum is shownin FIG. 3.

Further, as the result of measuring the NMR of the compound (c), theabove structure was supported. The content of the obtained NMR is asfollows:

δ=11.40 (s, 1H, phenol-OH), 8.69 (s, 1H, benzotriazole-H), 8.10 m, 1H,benzotriazole-H), 7.96 (m, 1H, benzotriazole-H), 7.80 (s, 1H, phenol-H),7.04 (s, 1H, phenol-H), 4.04 (s, 3H, benzotriazole-C—O—O—CH₃—H), 3.84(s, 3H, phenol-O—CH₃—H), 1.50 (s, 9H, tert-butyl-H)

Example 4 Synthesis of compound (d); octyl2-(3-tert-butyl-2-hydroxy-5-methoxyphenyl)-2H-benzotriazole-5-carboxylate

Compound (d) was obtained with the yield of 32% (from2-tert-butyl-4-methoxyphenyl) in the same manner as in Example 1 exceptthat octyl alcohol was used instead of methacrylate acid 2-hydroxyethyl.The melting point was 130° C. and the HPLC surface purity was 99.7%. Themaximum absorption wavelength A max was 312.8 nm and 379.8 nm,respectively, and the molar extinction coefficient ε of the wavelengthwas 14600 and 13000, respectively. The spectrum is shown in FIG. 4.

Further, as the result of measuring the NMR of the compound (d), theabove structure was supported. The content of the obtained NMR is asfollows.

δ=11.44 (s, 1H, phenol-OH), 8.71 (s, 1H, benzotriazole-H), 8.11 (d, 1H,J=1.5 Hz, benzotriazole-H), 7.97 (m, 1H, benzotriazole-H), 7.81 (s, 1H,phenol-H), 7.05 (s, 1H, phenol-H), 4.39 (m, 2H,benzotriazole-C—O—O—CH₂—H), 3.90 (s, 3H, phenol-O—CH₃—H), 1.50 (m, 21H,octyl-CH₂, tert-butyl-H), 0.90 (m, 3H, octyl-CH₃)

Example 5 Synthesis of compound (e); 2-ethylhexyl2-(3-tert-butyl-2-hydroxy-5-methoxyphenyl)-2H-benzotriazole-5-carboxylate

Compound (e) was obtained with the yield of 37% (from2-tert-butyl-4-methoxyphenyl) in the same manner as in Example 1 exceptthat 2-ethylhexyl alcohol was used instead of methacrylate acid2-hydroxyethyl. The melting point was 81° C. and the HPLC surface puritywas 99.8%. The maximum absorption wavelength λmax was 312.8 nm and 379.8nm, respectively, and the molar extinction coefficient ε of thewavelength was 15100 and 13100, respectively. The spectrum is shown inFIG. 5.

Further, as the result of measuring the NMR of the compound (e), theabove structure was supported. The content of the obtained NMR is asfollows.

δ=11.46 (s, 1H, phenol-OH), 8.73 (s, 1H, benzotriazole-H), 8.13 (d, 1H,J=9.0 Hz, benzotriazole-H), 7.97 (d, 1H, J=9.0 Hz, benzotriazole-H),7.82 (s, 1H, phenol-H), 7.05 (s, 1H, phenol-H), 4.32 (m, 2H,benzotriazole-C—O—O—CH₂—H), 3.90 (s, 3H, phenol-O—CH₃—H), 1.50 (m, 18H,tert-butyl-H, 2-ethylhexyl-CH₂, 2-ethylhexyl-CH), 0.96 (m, 6H,2-ethylhexyl-CH₃)

Example 6 Synthesis of compound (f); 2-methacyloyl oxyethyl2-(2-hydroxy-5-methoxyphenyl)-2H-benzotriazole-5-carboxylate

Compound (f) was obtained with the yield of 5% (from 4-methoxyphenyl) inthe same manner as in Example 1 except that 4-methoxyphenol was usedinstead of 2-tert-butyl-4-methoxyphenol. The melting point was 94° C.and the maximum absorption wavelength λ max was 309.8 nm and 373.2 nm,respectively, and the molar extinction coefficient ε of the wavelengthwas 14700 and 13100, respectively. The spectrum is shown in FIG. 6.

Further, by HPLC analysis, a purity of the compound (e) was measured.

<Condition of Measurement>

Apparatus: L-2130 (Hitachi High-Technologies Corporation)

Column used: Inertsil ODS-3 4.6×150 mm 5 μm

Column temperature: 25° C.

Mobile phase: acetonitrile/water=9/1 (phosphoric acid 3 ml/L)

Flow velocity: 1.0 ml/min

Detection: UV250 nm

<Result of Measurement>

HPLC surface purity: 93.4%

Further, as the result of measuring the NMR of the compound (f), theabove structure was supported. The content of the obtained NMR is asfollows.

δ=10.71 (s, 1H, phenol-OH), 8.73 (s, 1H, benzotriazole-H), 8.12 (d, 1H,J=9.6 Hz, benzotriazole-H), 7.98 (d, 1H, J=9.6 Hz, benzotriazole-H),7.15 (m, 3H, phenol-H), 6.18 (s, 1H, C═CH₂—H), 5.62 (s, 1H, C═CH₂—H),4.65 (m, 2H, methacryloyl-O—CH₂—H), 4.57 (m, 2H,benzotriazole-CO—O—CH₂—H), 3.89 (s, 3H, phenol-O—CH₃—H), 1.98 (s, 3H,CH₂═C—CH₃—H)

Comparative Example

As a comparative example, a compound (g);3-(2H-benzotriazole-2-yl)-4-hydroxyphenethyl methacrylate that is aconventionally general ultraviolet light absorber was synthesized.

(Preparation of a Light Absorbing Film)

0.1 g of compound (e) obtained in Example 5, 1.9 g of polymethylmethacrylate, 4.0 g of methylethylketone, and 4.0 g of toluene weremixed and dissolved to obtain a solution of a resin composition having alight absorber. Then the obtained solution of the resin compositionhaving a light absorber was applied onto a glass plate (2 mm thick) byusing a bar coater No. 20, followed by heating and drying at 90° C. for2 minutes, then followed by heating and drying at 120° C. for 3 minutes.After that, drying under reduced pressure was implemented at 40° C. for12 hours to remove the solvent thereby obtaining a film of polymethylmethacrylate having 5% light absorber with the film thickness of 4 μm.In the meantime, the compounds (g) synthesized in Comparative Examplewas copolymerized with methyl methacrylate to prepare a copolymer thatincludes 5% light absorber, followed by filming them by the same methodas in compound (e) thereby obtaining a film of polymethyl methacrylatehaving 5% light absorber with the film thickness of 4 μm.

[Light Blocking Test]

By placing the film of polymethyl methacrylate having 5% light absorberof the compounds (e) and (g) that were obtained in the above mentionedmethods on transfer films of yellow dyes, cyan dyes, and magenta dyes,that are used for commercially available sublimation transfer typecompact photo printer (Canon SELPHY CP600) to protect the transferfilms, followed by irradiating simulated solar light for 100 hours by aweather meter to see color fading. Five criteria were set in which Level5 signifies no fading, level 4 little fading, level 3 fading to someextent, level 2 much fading and level 1 complete fading. The resultsevaluated based on the above are shown in Table 1.

TABLE 1 Light absorbing Compound (g) No film film Compound (e)(Comparison) (Comparison) Evaluation 5 3 2 result of light blocking test

From Table 1, it is found that compared with the conventional lightabsorber, the product related to the present invention has higher lightblocking function for a long term, and therefore, it can be said thatthe product related to the present invention is a useful light absorber.For information, the condition of the light blocking test for the filmsin which the compound obtained from Examples and Comparative Example isas follows.

<Condition of Light Blocking Test>

Apparatus: Superxenon weather meter SX-75 (Suga Test Instruments Co.,Ltd)

Irradiation intensity: 180 W/m²

Irradiation time: 100 hours

Black panel temperature: 63° C.

Tank moisture: 50%

INDUSTRIAL AVAILABILITY

The benzotriazole derivative compound of the present invention exhibitsa maximum absorption wavelength in a vicinity of 310 nm and 380 nm, withexcellent ultraviolet light blocking function and excellent lightblocking function for a visible light short wavelength range, andtherefore, the light blocking function is not damaged even when exposedto solar light for a long time. Thus, it can be utilized for a materialthat deteriorates with ultraviolet light and the light of a visiblelight short wavelength range and for protection of a human body.

BRIEF EXPLANATION OF DRAWINGS

FIG. 1 shows UV-visible absorption spectrum of a compound (a).

FIG. 2 shows UV-visible absorption spectrum of a compound (b).

FIG. 3 shows UV-visible absorption spectrum of a compound (c).

FIG. 4 shows UV-visible absorption spectrum of a compound (d).

FIG. 5 shows UV-visible absorption spectrum of a compound (e).

FIG. 6 shows UV-visible absorption spectrum of a compound (f).

The invention claimed is:
 1. A benzotriazole derivative compoundrepresented by the following general formula (1):

wherein R₁ in the above general formula (1) is a hydrogen atom, or analkyl group whose carbon number is 1 to 8, wherein R₂ in the abovegeneral formula (1) is an alkyl group whose carbon number is 1 to 8, andwherein R₃ in the above general formula (1) is an acryloyl oxyalkylgroup whose alkyl carbon number is 1 to 2 or a methacryloyl oxyalkylgroup whose alkyl carbon number is 1 to
 2. 2. A light-absorber includingthe benzotriazole derivative compound according to claim
 1. 3. Alight-absorbing resin composition wherein the benzotriazole derivativecompound according to claim 1 is compounded in a resin.